CN109167034B - Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof - Google Patents

Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof Download PDF

Info

Publication number
CN109167034B
CN109167034B CN201810954803.9A CN201810954803A CN109167034B CN 109167034 B CN109167034 B CN 109167034B CN 201810954803 A CN201810954803 A CN 201810954803A CN 109167034 B CN109167034 B CN 109167034B
Authority
CN
China
Prior art keywords
sulfur
lithium
lini
positive electrode
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810954803.9A
Other languages
Chinese (zh)
Other versions
CN109167034A (en
Inventor
高学平
王璐
李国然
刘胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN201810954803.9A priority Critical patent/CN109167034B/en
Publication of CN109167034A publication Critical patent/CN109167034A/en
Priority to EP19852008.2A priority patent/EP3817101B1/en
Priority to PCT/CN2019/072446 priority patent/WO2020037948A1/en
Priority to US17/264,294 priority patent/US11958759B2/en
Application granted granted Critical
Publication of CN109167034B publication Critical patent/CN109167034B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a lithium-sulfur battery composite positive electrode material taking ternary material as a carrier and a preparation method thereof0.8Co0.15Al0.05)O2Or nickel cobalt manganese ternary material LiNixCoyMn1‑x‑yO2(0<x<1，0<y<1，0<x+y<1) The composite anode material is compounded, wherein the sulfur accounts for 50-80% of the composite anode material by mass percent. The carrier material has adsorption and catalysis effects on polar polysulfide, can realize sulfur fixation and the effect of promoting electrochemical reaction, and then obtains a lithium sulfur battery with high capacity and high stability.

Description

Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur battery electrode materials, and particularly relates to a lithium-sulfur battery composite positive electrode material taking a nickel-cobalt-aluminum or nickel-cobalt-manganese ternary material as a carrier and a preparation method thereof.
Background
In recent years, new energy automobiles increasingly enter the lives of people, and the development of the new energy automobiles is beneficial to optimizing energy structures and solving the environmental problems brought by traditional fuels. However, the development of new energy vehicles has not left a safe and reliable electrical energy storage system. As an efficient and clean energy storage system commonly used in new energy automobiles, an electrochemical cell is required to have not only high safety but also high energy density. Although the development potential of the electric vehicle is good at present, the ratio is still lower than 1%, one factor is the energy density of the battery, and the extreme value of the energy density of the electric vehicle with the lithium ion battery is only about 1/40 of an oil-burning automobile. Meanwhile, the battery pack occupies a large space in the vehicle due to the fact that the battery pack is too large in size due to the low volume energy density of the battery pack, and adverse effects are brought to the design and the driving experience of the new energy automobile. At present, the energy density of commercial lithium ion batteries can reach 200-250 Wh kg-1But still it is difficult to meet the explosive development of the industry. Therefore, in order to accelerate the development of new energy vehicles, optimize the conventional energy structure, and develop a new battery system with high energy density is forced to be in the eyebrowAnd (5) eyelash beating.
Two approaches are commonly used to increase the energy density of the battery, one is to reduce the parts that do not contribute to the capacity, such as current collectors, binders, etc.; the capacity of the positive and negative electrode active materials per unit mass or volume is increased. The first method has a limited effect on increasing the energy density of the battery, and therefore, it is critical to increase the energy density of the battery from the aspect of the positive and negative electrode active materials. The total molecular weight of the positive active material in the commercial lithium ion battery is large, and the number of transferred electrons corresponding to the electrode reaction is small, so that the improvement space of the lithium ion battery in the aspect of energy density is not large. The development of a light active material for multiple electron reactions is an effective way to greatly increase the Energy density of a battery (Energy)&Environmental Science,2010,3, 174-189). The lithium-sulfur battery using the elemental sulfur as the positive active material and the metallic lithium as the negative electrode utilizes the two-electron reaction between the sulfur and the lithium and the light weight characteristic of the sulfur and the lithium, and theoretically, the mass energy density can reach 2600Wh kg-1. Therefore, lithium-sulfur batteries are considered to be one of the most promising high specific energy secondary battery systems in the future. However, the inherent insulating property of elemental sulfur and the "shuttling effect" of soluble intermediates can result in reduced utilization of active materials in the battery and reduced cycle life of the battery. The sulfur simple substance is usually compounded with other conductive carbon materials to construct a sulfur/carbon composite anode material so as to improve the conductivity of an active substance, and the lithium polysulfide is physically adsorbed by utilizing the developed pore structure and the larger specific surface area of the carbon material, so that the cycle performance of the sulfur anode is improved to a certain extent. However, such physical adsorption hardly guarantees the long-term cycle stability of the battery. Meanwhile, the carbon material has small density and large specific surface area, which is not beneficial to the improvement of the volume energy density of the anode material, although the sulfur loading capacity of the high-sulfur-loading-capacity anode based on the carbon carrier can reach more than 10mg cm at present-2(Advanced Materials,2016,28, 3374-3382) but is usually a self-supporting structure prepared from carbon Materials such as graphene and carbon nanotubes, the electrode sheet cannot be rolled, the amount of electrolyte is increased by the gaps in the electrode sheet, and the problems of dissolution and shuttling of lithium polysulfide still exist.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lithium-sulfur battery composite positive electrode material taking a ternary material as a carrier, which utilizes the polar adsorption effect and the catalytic conversion effect of the ternary material on polar lithium polysulfide to slow down the diffusion and shuttle of the lithium polysulfide and improve the electrochemical stability of the lithium-sulfur battery.
In order to solve the above technical problems, according to an aspect of the present invention, a lithium-sulfur battery composite positive electrode material using a ternary material as a carrier is provided, which is composed of elemental sulfur and a nickel-cobalt-aluminum ternary material Li (Ni) as a carrier0.8Co0.15Al0.05)O2Or nickel cobalt manganese ternary material LiNixCoyMn1-x-yO2(0<x<1，0<y<1，0<x+y<1) The composite anode material is compounded, wherein the sulfur accounts for 50-80% of the composite anode material by mass percent.
Further, the nickel-cobalt-aluminum ternary material is of a layered structure and is spheroidal secondary particles formed by stacking sheet-shaped primary particles, and the particle diameter is 2-25 mu m; the tap density is 2.0-2.6 g cm-3。
Further, the nickel-cobalt-manganese ternary material is of a layered structure and is formed by stacking primary particles to form secondary particles, wherein the secondary particles are spherical-like and have the diameter of 2-25 mu m; the nickel-cobalt-manganese ternary material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2One kind of, LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2Have specific surface areas of 46.72, 10.90, 12.73 and 10.40m, respectively2g-1Tap densities of 2.09, 2.48, 2.46 and 2.56g cm-3。
According to another aspect of the present invention, there is provided a method for preparing the above lithium sulfur battery composite cathode material using the ternary material as a carrier, wherein the method for compounding elemental sulfur and the carrier includes a simple mixing method, a melting method, a vapor deposition method, a dissolution-crystallization method or a chemical deposition method.
Further, the simple mixing method is to mix and grind the elemental sulfur and the nickel-cobalt-aluminum ternary material or the nickel-cobalt-manganese ternary material according to a proportion to obtain the composite cathode material.
Further, the melting method comprises the steps of mixing and grinding elemental sulfur and a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material in proportion, placing the mixture in a reaction kettle, filling one or more of nitrogen, argon, helium and carbon dioxide, keeping the temperature at 100-200 ℃ for 2-20 hours, and finally cooling to room temperature to obtain the composite anode material.
Further, the vapor deposition method comprises the steps of mixing and grinding elemental sulfur and a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material in proportion, placing the mixture into a reaction kettle, filling one or more of nitrogen, argon, helium and carbon dioxide, preserving heat for 2-20 hours at 100-200 ℃, and then heating to 250-350 ℃ and preserving heat for 2-12 hours; and finally, cooling to room temperature to obtain the composite cathode material.
Further, the dissolving-crystallizing method is used for dissolving elemental sulfur in a solvent to prepare a solution, wherein the concentration range of sulfur in the solution is 1-20 mg mL-1And adding a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material according to a proportion, slowly stirring until a solvent volatilizes, drying and cooling the obtained solid to obtain the composite cathode material, wherein the solvent is one or more of carbon disulfide, carbon tetrachloride, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane, n-octane, tetrachloroethylene, trichloroethylene and tetrachloroethane.
Further, the chemical deposition method comprises the steps of uniformly mixing a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material with a sulfur-containing solution, slowly adding acid dropwise, reacting the sulfur-containing solution with the acid to generate a sulfur simple substance in situ, centrifuging and drying to obtain the composite cathode material, wherein the sulfur-containing solution is sodium thiosulfate or polysulfideOne of sodium dissolving solution with the concentration of 0.01-1 mol L-1(ii) a The acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and formic acid, and the concentration is 0.1-10 mol L-1The reaction time is 0.5-6 h.
According to another aspect of the present invention, there is provided a lithium sulfur battery comprising a positive electrode sheet prepared from the above-mentioned lithium sulfur battery composite positive electrode material using a ternary material as a carrier.
The invention utilizes nickel-cobalt-aluminum ternary material LiNi0.8Co0.15Al0.05O2And nickel cobalt manganese ternary material LiNixCoyMn1-x-yO2(0<x<1，0<y<1，0<x+y<1) The composite anode material is used as a carrier material and is compounded with elemental sulfur to obtain the composite anode material of the lithium-sulfur battery, the carrier material has adsorption and catalysis effects on polar polysulfide, and can realize the effects of fixing sulfur and promoting electrochemical reaction, so that the lithium-sulfur battery with high capacity and high stability is obtained.
Nickel-cobalt-aluminum ternary material LiNi0.8Co0.15Al0.05O2And nickel cobalt manganese ternary material LiNixCoyMn1-x-yO2(0<x<1，0<y<1，0<x+y<1) The lithium ion anode material is a commercial lithium ion anode material, has mature preparation process, easily obtained raw materials and higher tap density, and is more favorable for improving the volume energy density of the anode material compared with a sulfur/carbon composite anode material.
Drawings
FIG. 1 shows the cycle performance of the lithium-sulfur battery composite positive electrode materials prepared in examples 1 to 5 at a rate of 0.1C.
Fig. 2 is a step-rate cycle chart of the composite cathode material for a lithium-sulfur battery prepared in example 1.
FIG. 3 is an XRD pattern corresponding to examples 6-9.
FIG. 4 is a TG plot corresponding to examples 6 to 9 and comparative example 1.
FIG. 5 is a graph showing the discharge specific capacity at 0.1C rate of the lithium sulfur batteries of examples 6 to 9 and comparative example 1.
Fig. 6 is a graph of volumetric capacity density at 0.1C rate for the positive electrode materials of lithium sulfur batteries prepared in example 9 and comparative example 1.
Detailed Description
The invention provides a lithium-sulfur battery composite positive electrode material taking ternary material as a carrier, which is prepared from elemental sulfur and a nickel-cobalt-aluminum ternary material Li (Ni) as a carrier0.8Co0.15Al0.05)O2Or nickel cobalt manganese ternary material LiNixCoyMn1-x-yO2(0<x<1，0<y<1，0<x+y<1) The composite positive electrode material is formed by compounding, wherein the mass percentage content of sulfur in the composite positive electrode material is 50-80%, such as 50%, 55%, 60%, 65%, 70%, 75% and 80%.
According to the above embodiment, the carrier material is a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material of a commercial lithium ion battery positive electrode material, and the carrier material is compounded with sulfur to be used as the lithium sulfur battery positive electrode material, so that the raw materials are easily available, and the method is simple.
The nickel-cobalt-aluminum ternary material is used as a carrier material of sulfur in the positive electrode material of the lithium-sulfur battery, can generate strong adsorption and catalysis effects on lithium polysulfide, effectively inhibits the dissolution of the lithium polysulfide, and relieves the shuttle effect, so that the battery has the characteristics of high specific capacity and high cycle stability.
The nickel-cobalt-manganese ternary material is used as a carrier material of sulfur in the positive electrode material of the lithium-sulfur battery, and can have a strong chemical adsorption effect on polar lithium polysulfide; meanwhile, the nickel-cobalt-manganese ternary material has a catalytic conversion effect on lithium polysulfide, can reduce the lithium polysulfide into thiosulfate, promotes the conversion of the lithium polysulfide, inhibits the dissolution of the lithium polysulfide, slows down the shuttle effect, and then obtains the lithium-sulfur battery with high capacity and high stability.
The elemental sulfur is one or two of settled sulfur or sublimed sulfur, and the mesh number of the sulfur powder is 100-325 meshes.
In a preferred embodiment, the nickel-cobalt-aluminum ternary material is commercial lithium ion battery material Li (Ni)0.8Co0.15Al0.05)O2The preparation method of the corresponding precursor is a coprecipitation method, and the preparation process is mature and practicableThe preparation is carried out on a large scale.
The nickel-cobalt-aluminum ternary material is of a layered structure, is spherical secondary particles formed by stacking primary particles, has good sphericity, particle diameter of 2-25 mu m and small specific surface area, is convenient for industrially preparing a positive plate in a smear mode after being compounded with sulfur, and can obviously reduce the using amount of electrolyte, improve the energy density of a battery, reduce the manufacturing cost and improve the energy density of the battery.
The tap density of the nickel-cobalt-aluminum ternary material is high, and the measured value is 2.0-2.6 g cm-3. Mixing the nickel-cobalt-aluminum ternary material with sulfur according to the mass ratio of 30:70 to obtain S/Li (Ni)0.8Co0.15Al0.05)O2The tap density of the composite material is 1.5-2.0 g cm-3In contrast, the tap density of the sulfur/bp 2000 composite positive electrode material obtained by mixing the traditional commercial conductive carbon bp2000 and sulfur according to the ratio of 30:70 is 0.83g cm-3. S/Li (Ni) according to the invention0.8Co0.15Al0.05)O2The composite material has tap density higher than that of the S/bp2000 composite anode material. The nickel-cobalt-aluminum ternary material is used as the anode carrier material of the lithium-sulfur battery, so that the tap density of the anode material can be increased, and the volume energy density of the lithium-sulfur battery is further improved.
In a preferred embodiment, the nickel-cobalt-manganese ternary material is of a layered structure, and secondary particles are formed by stacking primary particles, wherein the secondary particles are spherical-like and have the diameter of 2-25 μm; the nickel-cobalt-manganese ternary material is selected from LiNi1/ 3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2One kind of, LiNi1/ 3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2Have specific surface areas of 46.72, 10.90, 12.73 and 10.40m, respectively2g-1Vibration ofThe solid densities were 2.09, 2.48, 2.46 and 2.56g cm-3。
The nickel-cobalt-manganese ternary material is a solid sphere formed by stacking primary particles, has a small specific surface area, and can reduce the using amount of electrolyte and improve the energy density of the battery compared with a nano material and a porous material.
Composite material S/LiNi obtained by compounding nickel-cobalt-manganese ternary material and sulfur1/3Co1/3Mn1/3O2、S/LiNi0.5Co0.2Mn0.3O2、S/LiNi0.6Co0.2Mn0.2O2And S/LiNi0.8Co0.1Mn0.1O2Has tap densities of 1.68, 1.77 and 1.81g cm-3The composite material has high tap density, and is favorable for obtaining the high-volume energy density anode material.
The ternary material can be compounded with sulfur simple substance by different preparation methods to obtain the composite cathode material for the lithium-sulfur battery with high sulfur content. In an exemplary embodiment of the present invention, a method for preparing a composite positive electrode material for a lithium sulfur battery using the ternary material as a carrier is provided, and the method for compounding elemental sulfur and the carrier includes a simple mixing method, a melting method, a vapor deposition method, a dissolution-crystallization method, or a chemical deposition method.
In a relatively specific embodiment, the simple mixing is to mix and grind elemental sulfur and a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material in proportion to obtain the composite cathode material.
For example, the simple mixing method described above may adopt one or more of grinding or ball milling, wherein the grinding time is 15-60 min; the ball milling time is 15-120 min, the ball milling rotation speed is 50-600 r/min, the ball material ratio is 1: 1-50: 1, and the ball milling solvent is one or more of water, methanol, ethanol, isopropanol and butanol.
In a relatively specific embodiment, the melting method is to mix and grind the elemental sulfur and the nickel-cobalt-aluminum ternary material or the nickel-cobalt-manganese ternary material in proportion and then place the mixture in a reaction kettle, and the reaction kettle is filled with air, nitrogen, argon and heliumAnd one or more of carbon dioxide and the carbon dioxide are sealed and then placed in a muffle furnace, the heat preservation temperature is set to be 100-200 ℃, the heat preservation time is controlled to be 2-20 hours, and finally the composite anode material is cooled to room temperature to obtain the composite anode material, wherein in the method, the temperature can be controlled to be 2 ℃ for min-1And the rate of temperature rise.
In a relatively specific embodiment, the vapor deposition method comprises the steps of mixing and grinding elemental sulfur and a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material in proportion, placing the mixture into a reaction kettle, filling one or more of nitrogen, argon, helium and carbon dioxide, keeping the temperature for 2-20 hours at 100-200 ℃, and then heating to 250-350 ℃ and keeping the temperature for 2-12 hours; and finally, cooling to room temperature to obtain the composite cathode material. In the above method, the temperature can be 2 deg.C for min-1And the rate of temperature rise.
In a relatively specific embodiment, the dissolving-crystallizing method dissolves elemental sulfur in a solvent to prepare a solution, wherein the concentration of sulfur in the solution is 1-20 mg mL-1And then adding a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material according to a proportion, slowly stirring until a solid obtained by solvent volatilization is dried and cooled to obtain the composite cathode material, wherein the solvent is one or a combination of more of carbon disulfide, carbon tetrachloride, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane, n-octane, tetrachloroethylene, trichloroethylene and tetrachloroethane.
In a relatively specific embodiment, the chemical deposition method comprises the steps of uniformly mixing a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material with a sulfur-containing solution, slowly dropwise adding an acid, reacting the sulfur-containing solution with the acid to generate a sulfur simple substance in situ, centrifuging, and drying to obtain the composite cathode material, wherein the sulfur-containing solution is one of sodium thiosulfate and sodium polysulfide solution, and the concentration of the sulfur-containing solution is 0.01-1 mol L-1(ii) a The acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and formic acid, and the concentration is 0.1-10 mol L-1The reaction time is 0.5-6 h.
Preferably, the elemental sulfur is one or two of settled sulfur and sublimed sulfur, and the mesh number of the sulfur powder is 100-325 meshes.
In another exemplary embodiment of the present invention, a lithium sulfur battery is provided, which includes a positive electrode sheet prepared from the above-mentioned lithium sulfur battery composite positive electrode material using a ternary material as a carrier. The positive plate can be prepared by adopting a smear method. For example, the composite cathode material, conductive carbon black and polyvinylidene fluoride (PVdF) are added into N-methyl pyrrolidone (NMP), and stirred to obtain cathode slurry; coating the slurry on an aluminum foil, and drying in a drying box; and finally cutting the positive plate into a wafer.
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Examples 1 to 5 relate to S/Li (Ni)0.8Co0.15Al0.05)O2A preparation method of the composite positive electrode material and a lithium-sulfur battery prepared based on the composite positive electrode material.
Example 1
Mixing Li (Ni) as Ni-Co-Al ternary material0.8Co0.15Al0.05)O2Uniformly mixing the sulfur and the elemental sulfur according to the mass ratio of 30:70, and then preserving heat for 12 hours at 155 ℃ in an argon atmosphere to obtain S/Li (Ni)0.8Co0.15Al0.05)O2-1 composite positive electrode material.
The prepared composite anode material is made into an electrode slice according to the following method, and a battery is assembled for testing:
weighing the prepared composite positive electrode material S/Li (Ni) according to the mass ratio of 70:20:100.8Co0.15Al0.05)O 21, Super P and PVdF, uniformly mixing, adding a proper amount of NMP, and stirring for 4 hours to obtain positive electrode slurry with proper viscosity (the Super P, the PVdF and the NMP are all conventional reagents in the field); coating the slurry on an aluminum foil, and drying in a drying oven at 60 ℃ for 12 hours for later use; cutting the obtained positive plate into circular sheets with the diameter of 10mm, and assembling the circular sheets into buttons in a glove box filled with argonThe amount of electrolyte used was 10. mu.L per mg of sulfur. And after the battery is kept stand for 4 hours, testing the battery on a battery testing system by a charging and discharging program with the voltage range of 0.1C multiplying power and 1.7-2.8V. The specific discharge capacity of the battery was calculated by the mass of sulfur, and the variation of the discharge capacity with the number of cycles was shown in fig. 1, and the relevant data are shown in table 1. In addition, the battery was subjected to a step-rate charge/discharge test, S/Li (Ni)0.8Co0.15Al0.05)O2The step-rate cycling of the composite for lithium sulfur batteries is shown in FIG. 2.
Example 2
Mixing Li (Ni)0.8Co0.15Al0.05)O2Uniformly mixing the sulfur and the elemental sulfur according to the mass ratio of 30:70, then preserving heat for 8 hours at 155 ℃ in the argon atmosphere, then heating to 300 ℃, and preserving heat for 6 hours to obtain S/Li (Ni)0.8Co0.15Al0.05)O2-2 composite positive electrode material.
The obtained composite cathode material S/Li (Ni)0.8Co0.15Al0.05)O2-2 electrodes were made as in example 1 and assembled into battery tests, using 10 μ L electrolyte (per mg of sulphur). The specific discharge capacity of the battery was calculated as the mass of sulfur. Electrochemical performance testing of the cells was performed as in example 1. The variation of discharge capacity with cycle number is shown in fig. 1, and the relevant data are shown in table 1.
Example 3
Mixing Li (Ni)0.8Co0.15Al0.05)O2Mixing the sulfur with the elemental sulfur according to a mass ratio of 30:70, uniformly grinding, and controlling the grinding time to be 15-60 min to obtain S/Li (Ni)0.8Co0.15Al0.05)O2-3 composite positive electrode material.
The obtained composite cathode material S/Li (Ni)0.8Co0.15Al0.05)O2-3 electrodes were made as in example 1 and assembled into battery tests, using 10 μ L electrolyte (per mg of sulphur). The specific discharge capacity of the battery was calculated as the mass of sulfur. Specific electrochemical performance tests were performed as in example 1. The variation of discharge capacity with cycle number is shown in fig. 1, and the relevant data are shown in table 1.
Example 4
Elemental sulfur was added at 5mg mL-1In a ratio of (A) to (B) in CS2Stirring until dissolved, adding Li (Ni) with the mass ratio of 30:70 to sulfur0.8Co0.15Al0.05)O2Slowly stirring at 60 deg.C until the solvent volatilizes, vacuum drying the obtained solid, and cooling to obtain S/Li (Ni)0.8Co0.15Al0.05)O2-4 composite positive electrode material.
The obtained composite cathode material S/Li (Ni)0.8Co0.15Al0.05)O2-4 electrodes were made as in example 1 and assembled into battery tests, using 10 μ L electrolyte (per mg of sulphur). The specific discharge capacity of the battery was calculated as the mass of sulfur. Electrochemical performance testing of the cells was performed as in example 1. The variation of discharge capacity with cycle number is shown in fig. 1, and the relevant data are shown in table 1.
Example 5
0.03mol of sodium thiosulfate was dissolved in 200mL of water (containing 1 wt.% PVP) and 0.24g of Li (Ni) was added0.8Co0.15Al0.05)O2Then 30ml of dilute hydrochloric acid (5 wt.%) is slowly added dropwise, the sodium thiosulfate reacts with the hydrochloric acid to obtain elemental sulfur, which is deposited on Li (Ni)0.8Co0.15Al0.05)O2The solution is centrifuged, washed and dried to obtain S/Li (Ni)0.8Co0.15Al0.05)O2-5 composite positive electrode material.
The obtained composite cathode material S/Li (Ni)0.8Co0.15Al0.05)O2-5 electrodes were made as in example 1 and assembled into cell tests with an electrolyte dosage of 10 μ L. The specific discharge capacity of the battery was calculated as the mass of sulfur. Electrochemical performance testing of the cells was performed as in example 1. The variation of discharge capacity with cycle number is shown in fig. 1, and the relevant data are shown in table 1.
It can be seen from the cycle performance diagram (fig. 1) of the composite positive electrode material for lithium-sulfur batteries prepared in examples 1 to 5 at a magnification of 0.1C that the melting method, the vapor deposition method, the simple mixing method, and the dissolution-bonding method are adoptedS/Li (Ni) prepared by five different modes of crystallization and precipitation0.8Co0.15Al0.05)O2The composite positive electrode materials all show excellent cycle performance, which shows that the nickel-cobalt-aluminum ternary material adopted as the carrier material of the sulfur positive electrode of the lithium-sulfur battery can well play a role in sulfur fixation, and the nickel-cobalt-aluminum ternary material is mainly derived from a polar oxide, can adsorb polysulfide ions by virtue of a chemical bonding effect, slows down a shuttle effect and improves the cycle stability of the battery; as can be seen from the cycle curve at step rate of the composite cathode material prepared in example 1 of FIG. 2, S/Li (Ni) for lithium sulfur battery0.8Co0.15Al0.05)O2The rate capability of the composite anode material is superior; meanwhile, the tap density of the nickel-cobalt-aluminum ternary material is high, so that the tap density of the anode material can be improved after the nickel-cobalt-aluminum ternary material is compounded with sulfur, and the energy density of the battery can be increased; the battery still obtains better cycle performance when the using amount of the electrolyte is lower (10 mu L), which shows that the smaller specific surface area of the nickel-cobalt-aluminum ternary material is beneficial to reducing the using amount of the electrolyte and improving the integral energy density of the battery.
Embodiments 6-11 relate to a method for preparing a composite positive electrode material for a sulfur/nickel cobalt manganese ternary material lithium sulfur battery and a lithium sulfur battery prepared based on the composite positive electrode material.
Example 6
The nickel-cobalt-manganese ternary material is adopted as the LiNi which is a commercial lithium ion battery anode material1/3Co1/3Mn1/3O2Wherein the ratio of nickel, cobalt and manganese is 1:1:1, and the XRD spectrogram of the material is shown in figure 3. Reacting LiNi1/3Co1/3Mn1/3O2Mixing with sulfur at a mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, placing the reaction kettle in a muffle furnace at 2 deg.C for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; finally cooling to room temperature to obtain the composite positive electrode material S/LiNi of the lithium-sulfur battery1/3Co1/3Mn1/3O2. The sulfur content thereof was 69.67 wt% as measured by TG, as shown in FIG. 4.
The prepared composite positive electrode material is manufactured into an electrode plate according to the following processes and assembled into a battery for testing:
(1) electrode plate manufacturing
The composite cathode material S/LiNi1/3Co1/3Mn1/3O2Adding conductive carbon black and polyvinylidene fluoride (PVdF) into N-methyl pyrrolidone (NMP) according to a mass ratio of 70:20:10, and stirring for 4 hours to obtain positive electrode slurry (the PVdF and the NMP are both common reagents in the field); coating the slurry on an aluminum foil, and drying in a drying oven at 60 ℃ for 12 hours; finally, cutting the positive plate into a wafer with the diameter of 10 mm;
(2) battery assembly
The battery was assembled in a glove box under argon atmosphere and the button cell (2032 type) was assembled in the order "negative electrode can-tab-gasket-lithium sheet-diaphragm-electrolyte-positive electrode sheet-positive electrode can", electrolyte usage was 10 μ L (per mg of sulfur), positive electrode sheet diameter was 10mm, diaphragm diameter was 16mm, and lithium sheet diameter was 14 mm.
(3) Cycle performance test
Standing the assembled battery for 6h, and performing constant current charge and discharge test, wherein the voltage range is selected to be 1.7-2.8V, and the current density is set to be 0.1C (1C is 1675mA g)-1) And calculating the specific discharge capacity of the battery according to the mass of the sulfur to obtain a cycle performance curve of the battery, as shown in fig. 5. The specific discharge capacity of the battery was calculated as the mass of sulfur. Specifically, the specific first-cycle discharge capacity of the composite positive electrode material in example 6 was 1255.0mAh g-1The specific discharge capacity after 50 times of circulation is 1050.3mAh g-1The capacity retention rate was 83.7%.
Example 7
The nickel-cobalt-manganese ternary material is adopted as the LiNi which is a commercial lithium ion battery anode material0.5Co0.2Mn0.3O2Wherein the ratio of nickel, cobalt and manganese is 5:2:3, and the XRD spectrogram of the material is shown in figure 3. Reacting LiNi0.5Co0.2Mn0.3O2Mixing with sulfur at a mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, placing the reaction kettle in a muffle furnace at 2 deg.C for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; finally cooling to room temperature to obtain the composite cathode material S/LiNi0.5Co0.2Mn0.3O2. The sulfur content, as measured by TG, was 71.25 wt%, as shown in FIG. 4.
The prepared composite positive electrode material was used to prepare an electrode sheet according to the procedure described in example 6, and a battery was assembled according to the method described in example 6. The specific discharge capacity of the battery was calculated as the mass of sulfur. Specifically, the first cycle specific discharge capacity of the composite positive electrode material obtained in example 7 was 1308.1mAh g-1The specific discharge capacity after 50 times of circulation is 968.5mAh g-1The capacity retention rate was 74.0%.
Example 8
The nickel-cobalt-manganese ternary material is adopted as the LiNi which is a commercial lithium ion battery anode material0.6Co0.2Mn0.2O2Wherein the ratio of nickel, cobalt and manganese is 6:2:2, and the XRD spectrogram of the material is shown in figure 3. Reacting LiNi0.6Co0.2Mn0.2O2Mixing with sulfur at a mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, placing the reaction kettle in a muffle furnace at 2 deg.C for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; finally cooling to room temperature to obtain the composite cathode material S/LiNi0.6Co0.2Mn0.2O2. The sulfur content as measured by TG was 69.01 wt%, as shown in FIG. 4.
The prepared composite positive electrode material was used to prepare an electrode sheet according to the procedure described in example 6, and a battery was assembled according to the method described in example 6. The specific discharge capacity of the battery was calculated as the mass of sulfur. Specifically, the specific first-cycle discharge capacity of the composite positive electrode material obtained in example 8 was 1037.4mAh g-1The specific discharge capacity after 50 times of circulation is 1048.1mAh g-1The capacity retention rate was 80.2%.
Example 9
The nickel-cobalt-manganese ternary material is adopted as the LiNi which is a commercial lithium ion battery anode material0.8Co0.1Mn0.1O2Wherein the ratio of nickel, cobalt and manganese is 8:1:1, and the XRD spectrogram of the material is shown in figure 3. Reacting LiNi0.8Co0.1Mn0.1O2Mixing with sulfur simple substance in a mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, and placing the reaction kettle into a reaction kettleIn a muffle furnace at 2 ℃ for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; finally cooling to room temperature to obtain the composite cathode material S/LiNi0.8Co0.1Mn0.1O2. The sulfur content as measured by TG was 69.01 wt%, as shown in FIG. 4. The tap density of the composite material was 1.81g cm-3。
Electrode sheets were prepared from the composite positive electrode material prepared in example 9 as described in example 6, and battery tests were assembled as described in example 6. The specific discharge capacity of the battery was calculated as the mass of sulfur. Specifically, the first cycle specific discharge capacity of the composite positive electrode material obtained in example 9 was 1302.9mAh g-1The specific discharge capacity after 50 times of circulation is 1052.0mAh g-1The capacity retention rate was 81.4%.
Example 10
The difference from example 6 is that LiNi1/3Co1/3Mn1/3O2Mixing the lithium sulfur battery anode material with sulfur simple substance according to the mass ratio of 50:50 to obtain the composite anode material S/LiNi of the lithium sulfur battery1/3Co1/3Mn1/3O2Electrode sheet fabrication, cell assembly and testing was performed according to example 6. The specific first-cycle discharge capacity of the composite positive electrode material obtained in example 10 was 1268.9mAh g-1The specific discharge capacity after 50 times of circulation is 922.6mA h g-1The capacity retention rate was 72.7%.
Example 11
The difference from example 8 is that LiNi is used0.6Co0.2Mn0.2O2Mixing the lithium sulfur battery anode material with sulfur simple substance according to the mass ratio of 20:80 to obtain the composite anode material S/LiNi of the lithium sulfur battery0.6Co0.2Mn0.2O2Electrode sheet fabrication, cell assembly and testing was performed according to example 8. The specific first-cycle discharge capacity of the composite positive electrode material obtained in example 11 was 1174.8mAh g-1The specific discharge capacity after 50 times of circulation is 919.7mAh g-1The capacity retention rate was 78.3%.
Comparative example 1
For comparison, the invention provides a composite cathode material for an S/bp2000 lithium-sulfur battery, wherein bp2000 is one of common commercial conductive carbons, and the composite cathode material is prepared by the following steps:
mixing commercial conductive carbon bp2000 and sulfur elementary substance according to a mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, placing the reaction kettle into a muffle furnace at 2 ℃ for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; and finally, cooling to room temperature to obtain the composite anode material S/bp 2000. The sulfur content, as measured by TG, was 72.3 wt%, as shown in FIG. 4.
The composite positive electrode material prepared in comparative example 1 was used to fabricate an electrode tab by the procedure described in example 6, and a battery test was assembled by the method described in example 6. The specific discharge capacity of the battery was calculated as the mass of sulfur. Specifically, the first-cycle specific discharge capacity of the composite positive electrode material obtained in comparative example 1 was 1163.3mAh g-1The specific discharge capacity after 50 times of circulation is 818.3mAh g-1The capacity retention rate was 70.3%.
TABLE 1 comparison of Battery cycling Performance for examples 1-9
Figure BDA0001772426040000121
As can be seen from table 1 and fig. 5, the sulfur/nickel-cobalt-manganese ternary material composite positive electrode material prepared by loading sulfur on the nickel-cobalt-manganese ternary material provided by the invention shows a better capacity retention rate, which is much higher than that of the sulfur-carbon positive electrode material prepared based on commercial conductive carbon bp 2000. This shows that the nickel-cobalt-manganese ternary material has a strong chemical adsorption effect on lithium polysulfide and can inhibit the shuttle effect, thereby obtaining the composite cathode material with high capacity and high cycle stability. As can be seen from fig. 6, since the tap density of the nickel-cobalt-manganese ternary material is high, the volume capacity density of the sulfur positive electrode composite material using the ternary material as a support material is much higher than that of the sulfur-carbon composite material. Meanwhile, the nickel-cobalt-manganese ternary material has a smaller specific surface area, so that the using amount of electrolyte can be reduced, and the overall energy density of the battery is improved. It is apparent that the preferred embodiments of the present invention should not be limited to the present invention, and the appended claims should be construed to include the preferred embodiments and all such variations and modifications as fall within the scope of the invention.

Claims (2)

1. A lithium-sulfur battery composite positive electrode material taking a ternary material as a carrier is characterized in that: consists of elemental sulfur and nickel-cobalt-manganese ternary material LiNi as carrierxCoyMn1-x-yO2(x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is more than 0 and less than 1) are compounded;
mixing the carrier and sulfur simple substance according to the mass ratio of 30:70, grinding, transferring into a reaction kettle, sealing, placing the reaction kettle into a muffle furnace at the temperature of 2 ℃ for min-1The temperature is raised to 155 ℃ at the speed rate, and the temperature is kept for 12 hours; finally, cooling to room temperature to obtain the lithium-sulfur battery composite positive electrode material;
the nickel-cobalt-manganese ternary material is of a layered structure and is formed by stacking primary particles to form secondary particles, wherein the secondary particles are spherical-like and have the diameter of 2-25 mu m; the nickel-cobalt-manganese ternary material is selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2One kind of, LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2And LiNi0.8Co0.1Mn0.1O2Have specific surface areas of 46.72, 10.90, 12.73 and 10.40m, respectively2g-1Tap densities of 2.09, 2.48, 2.46 and 2.56gcm, respectively-3。
2. A lithium sulfur battery characterized by: the lithium-sulfur battery positive electrode plate comprises a positive electrode plate prepared from the lithium-sulfur battery composite positive electrode material taking the ternary material as a carrier in claim 1.
CN201810954803.9A 2018-08-21 2018-08-21 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof Active CN109167034B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201810954803.9A CN109167034B (en) 2018-08-21 2018-08-21 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
EP19852008.2A EP3817101B1 (en) 2018-08-21 2019-01-19 Lithium-sulfur battery composite anode material using ternary material as carrier and preparation method for lithium-sulfur battery composite anode material
PCT/CN2019/072446 WO2020037948A1 (en) 2018-08-21 2019-01-19 Lithium-sulfur battery composite anode material using ternary material as carrier and preparation method for lithium-sulfur battery composite anode material
US17/264,294 US11958759B2 (en) 2018-08-21 2019-01-19 Ternary oxide based composite cathode material for lithium-sulfur battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810954803.9A CN109167034B (en) 2018-08-21 2018-08-21 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109167034A CN109167034A (en) 2019-01-08
CN109167034B true CN109167034B (en) 2021-07-23

Family

ID=64896332

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810954803.9A Active CN109167034B (en) 2018-08-21 2018-08-21 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof

Country Status (4)

Country Link
US (1) US11958759B2 (en)
EP (1) EP3817101B1 (en)
CN (1) CN109167034B (en)
WO (1) WO2020037948A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167034B (en) * 2018-08-21 2021-07-23 南开大学 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
CN114212834B (en) * 2021-11-12 2024-01-30 汕头大学 Metal-doped modified ternary positive electrode material and preparation method thereof
CN114361712A (en) * 2022-01-07 2022-04-15 南京大学 Ternary material functional diaphragm of lithium-sulfur battery and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108281633A (en) * 2018-01-26 2018-07-13 南开大学 Lithium sulfur battery anode material, preparation method and lithium-sulfur cell

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102610803B (en) * 2012-03-27 2014-04-09 电子科技大学 Composite positive pole material for lithium ion battery and preparation method of composite material
DE102014003128A1 (en) * 2014-03-03 2015-09-03 Hochschule Aalen composite material
CN105047885B (en) * 2015-06-03 2017-11-28 徐茂龙 A kind of lithium sulfur battery anode material with high circulation performance and preparation method thereof
CN105206805A (en) * 2015-08-31 2015-12-30 无锡市嘉邦电力管道厂 Lithium sulfur battery positive electrode material preparing method and lithium sulfur battery prepared by using lithium sulfur battery positive electrode material
CN105529446A (en) * 2016-01-20 2016-04-27 中南大学 Lithium-sulfur battery composite positive electrode material and preparation method and application therefor
CN106410194A (en) * 2016-11-25 2017-02-15 上海空间电源研究所 Composite lithium battery and preparation method thereof
CN109167034B (en) * 2018-08-21 2021-07-23 南开大学 Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108281633A (en) * 2018-01-26 2018-07-13 南开大学 Lithium sulfur battery anode material, preparation method and lithium-sulfur cell

Also Published As

Publication number Publication date
EP3817101A1 (en) 2021-05-05
CN109167034A (en) 2019-01-08
EP3817101B1 (en) 2022-11-30
US20210300781A1 (en) 2021-09-30
WO2020037948A1 (en) 2020-02-27
EP3817101A4 (en) 2021-08-11
US11958759B2 (en) 2024-04-16

Similar Documents

Publication Publication Date Title
CN106920964B (en) Prussian blue type sodium ion battery positive electrode material and preparation method thereof
CN108232115B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN107845781B (en) Negative electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery
CN108281633B (en) Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
WO2020164353A1 (en) Porous carbon nanocomposite material doped with metal atoms and preparation method therefor and use thereof
CN112018344B (en) Carbon-coated nickel sulfide electrode material and preparation method and application thereof
CN109167034B (en) Lithium-sulfur battery composite positive electrode material taking ternary material as carrier and preparation method thereof
CN108054350B (en) Lithium-sulfur battery composite positive electrode material and preparation method thereof
CN110416530B (en) Flower-like manganese dioxide/carbon composite material and preparation method and application thereof
WO2024119936A1 (en) Positive electrode active material and use thereof
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN111029560A (en) Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof
CN112290001A (en) Molybdate-based sulfur-based composite positive electrode material and preparation method thereof
CN114702013B (en) Sodium ion battery metal selenide anode material and preparation method and application thereof
CN112768656A (en) Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof
CN112838198A (en) Water-based zinc ion battery positive electrode material, preparation method thereof and water-based zinc ion battery
CN114551794B (en) Positive electrode active material, positive electrode, preparation method and lithium ion battery
Kang et al. Shape control of hierarchical lithium cobalt oxide using biotemplates for connected nanoparticles
CN108899473B (en) High-performance flexible lithium secondary battery positive electrode and preparation method thereof
CN114927667B (en) Positive electrode active material, preparation method thereof, positive electrode sheet and lithium ion secondary battery
CN106972171B (en) Three-dimensional network structure material, preparation method and application thereof
CN114938686B (en) Lithium cobalt oxide layered anode material and preparation method and application thereof
CN111446439B (en) S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery
WO2018195837A1 (en) Metal-sulfur battery and preparation method therefor
CN111348640A (en) Porous carbon-Fe3O4Nanomaterial, air positive electrode material and lithium-air battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant